Condensation product of an aminotriazole, an aldehyde, and a halogenated amide



Patented Oct. 19, 1943 TRIAZOLE, AN ALDE GENATED AMIDE HYDE, AND A HALO-Gaetano F. DAlelio, Pittsfield, Mass, assignor to General ElectricCompany, a corporation of New York No Drawing. Application October 21,1941, Serial N 0. 415,938

20 Claims.

This invention relates to new condensation products and to methods ofmaking the same. The invention is concerned more particularly withself-curing aminoplasts, by which are'meant heat-convertible resinouscondensation products prepared from amino or amido compounds and havingthe characteristic property of curing under heat or under heat andpressure without the addition of a curing accelerator or catalyst.

In my copending application Serial No. 289,277, filed August 9, 1939,now Patent No. 2,285,418, issued June 9, 1942, and assigned to the sameas signee as the present invention, I disclosed and claimed new anduseful compositions of matter comprising a condensation product ofingredients comprising (1) a urea, specifically the compoundcorresponding to the formula CO(NH2)2, (2) an aliphatic aldehyde, e. g.,formaldehyde, and (3) certain halogenated amides, more particularlychlorinated acetamides. The present invention is directed to new anduseful condensation products wherein an aminotriazole (amidogentriazole)is caused to react with an aldehyde in the presence of a halogenatedamide of the kind hereafter mentioned.

In the production of aminoplasts it has heretofore been common practicein converting such materials to the insoluble, infusible state toincorporate into the condensation product or into the moldingcomposition a latent or an active (direct) curing catalyst. As pointedout more particularly hereafter, this technique and the final productshave not been wholly satisfactory.

I have discovered that self-curing aminoplasts can be produced bycondensing an aminotriazole (that is, an aldehyde-reactableaminotriazole), an aldehyde, including polymeric aldehydes andaldehyde-addition products, and a halogenated amide selected from theclass consisting of alpha halogenated amides, beta halogenated amidesand alpha beta halogenated amides, which amides contained at least one-CNH2 grouping. Examples of such halogenated amides are the halogenatedacetamides, more particularly the mono-, diand tri-chloracetamides, themono-, diand tri-bromoacetamides, the mono-, diand tri-iodoacetamides,the'mono-, diand tri-fluoroacetamides, and similar halogeno.derivativesof other amidated monocarboxylic and polycarboxylic acids such aspropionic, butyric, valeric, malonic, adipic, maleic, itaconic, fumaric,tricarballylic, etc., acids. In all cases the amide grouping of thehalogenated amide is capable of reaction with the aldehydic component,-since this amide grouping possesses a nitrogen atom to which areattached two hydrogen atoms.

It has been suggested heretofore that aminotriazolealdehyde condensationproducts by modified by incorporating therein an amide, specificallyurea, thiourea, dicyandiamide and thelike. However, to the best of myknowledge and belief it was not known or suggested prior to my inventionto intercondense an alpha halogenated amide, a beta halogenated amide oran alpha, beta halogenated amide, which amides contain at least oneCONH: grouping, with an aminotriazole and an aldehyde thereby to obtainan inter-condensation product of accelerated curing characteristics. Iam aware that it was suggested prior to my invention to prepareurea-formaldehyde molding compositions containing various compoundscapable of developing acidity during the molding operation and thatiso-di-brom succinic anilide specifically has been mentioned as acompound having this characteristic property. Iso-dibrom succinicanilide is difierent from, and is not the equivalent of, the halogenatedamides used in carrying the present invention into effect. Salts of themonoand di-halogenated aliphatic carboxylic acids, for example sodiumand ammonium mono-chloroacetates, also have been suggested as additionagents to urea-formaldehyde molding compositions to yieldheat-convertible masses that cure to an insoluble, infusible state underthe heat and pressure of molding. Such salts likewise are entirelydifierent from, and are not the equivalent of, the halogenated amidesrequired for practicing the present invention. These salts are latentcatalysts and, unlike the amides which I use, are incapable ofvcondensation with an aldehyde.

In the heat-convertible resinous condensation products of this inventionthe self-curing property of the product is imparted thereto by creatinga resin molecule having this inherent characteristic. This is adiscovery of great practical significance. It Jmakes possible theproduction of molding compositions of uniform curingcharacteristics,which compositions yield molded articles free from imperfections, suchas blisters, discolorations, etc. Such imperfections are due usually tolocalized curing that often occurs in aminoplasts of theadmixed-catalyst type. As

the value of the molded article, especially lightcolored articles, ismaterially influenced by its appearance, it is clear that the discoveryof any means for decreasing or eliminating entirely the production ofimperfect articles that must be scrapped or sold at reduced prices is ofconsiderable commercial importance.

The resin syrups and molding compositions of this invention may bestored for long periods of time without material alteration. In markedcontrast the prior heat-convertible aminoplasts of theaminotriazole-aldehyde type, more particularly those containing director active curing catalysts such as acids, for example hydrochloric,ethyl sulfuric, phthalic, chloroacetic, phosphoric, etc., lacked time orstorage stability. This necessitated early use of the material afterincorporating the catalyst.

Furthermore, the molding compositions of this invention cure rapidlyunder heat or under heat and pressure and have good plastic flow duringmolding. Hence molded articles of even the most complicated designs canbe produced rapidly and economically. The cured products have good lightstability, excellent water resistance and surface finish and, ingeneral, meet the strength, hardness and other requirements of theparticular service application.

In carrying the present invention into effect the condensation reactionbetween the aldehyde and r the other components preferably is startedunder neutral or alkaline conditions. Neutral conditions may beestablished by neutralizing (if necessary) either the mixed componentsor the individual'component or componentssprior to admixture. Anysubstance yielding an alkaline aqueous solution may be used in obtainingalkaline conditions for the initial condensation reaction. In

some cases it may be desirable, in order more quickly to initiatereaction between the starting materials, to add a small amount of asuitable organic or inorganic acid. Thereafter the solution is treatedto eliminate acidic conditions due to acid or acid salts. That is, themass is neutralized or is made alkaline by adding an alkaline substance.The reaction then is caused to proceed further to produce theself-curingaminoplasts of this invention.

In obtainingthe neutral, alkaline or acid conditions above described Imay use, for example, ammonia, sodium hydroxide or carbonate, calciumhydroxide, methylamine, diethyl amine, triisopropyl amine, ethanolamines, tri-isopropanol amine, etc., mixtures of such alkalinesubstances, inorganic or organic acids such as hydrochloric, sulfuric,phosphoric, acetic, acrylic, rotonic, malonic, etc., or acid salts suchas sodium acid sulfate, monosodlum phosphate, monosodium phthalate,etc., or mixtures of acids, of acid salts, or of acids and acid salts.

Various ways may be employed for effecting initial reaction between thecomponents. For example, I may first mix all the reactants and effectcondensation between the mixed reactants in the presence or absence ofaddition agents, as for instance condensation catalysts, fillers,plasticizers, other natural or synthetic resinous bodies,

solvents or diluents, etc. A preferred method is to add the halogenatedamide to a partial condensation product of an aminotriazole and analdehyd and eflect further condensation between the components. Inproducing such a paras alcohol, glycol, glycerine, water, etc.

ondary amines (e. g., dipropyl amine, dibutyl amine, etc.). Thesecondary condensation cata-' lyst, which ordinarily is used in anamount less than the amount of the primary catalyst, should be a fixedalkali, for instance a carbonate cyanide or hydroxide of an alkali metal(e. sodium, potassium, lithium, etc.)

Another method of eiiecting reaction between the ingredients comprisesfirst condensing the halogenated amide with the aldehyde, adding theresulting partial condensation product to an aminotriazole-aldehydepartial condensation product and then causing the reaction to proceedfurther. Or, I may condense or partially condense the halogenated amidewith a mol excess of an aldehyde, add an aminotriazole to thiscondensation product and effect further reaction between the components.Still other ways may be employed in combining the components and inproducing the unmodified and modified condensation products of thisinvention, as will be readily understood by those skilled in the art asthe description of the invention proceeds. These condensation reactionsmay proceed under a wide variety of time, temperature and pressureconditions.

The temperature of the reaction may vary from room temperature'to thereflux temperature of the reactants at reduced, atmospheric orsuperatmospheric pressures.

The products obtained as described above properly may be designated asintermediate condensation products. They are heat-convertible resinousbodies which alone or mixed with fillers, pigments, dyes, lubricants,plasticizers, etc., may be used, for example, as molding compositions.The

modified and unmodified resinous masses are selfconvertible under heator under heat and pressure to the insoluble, iniusible state.

Depending upon the particular reactants employed and the particularconditions of reaction, the intermediate I condensation products varyfrom clear, colorless, syrupy, water-soluble liquids to viscous, milkydispersions and gel-like masses of decreased solubility in ordinarysolvents, such These liquid intermediate condensation products may beconcentrated or diluted further by the removal or addition of volatilesolvents to form liquid coating compositions of adjusted viscosity andconcentration. These liquid compositions may be used, for instance,as'surface-coating materials, in the production of paints, varnishes,lacquers, enamels, etc., for general adhesive applications, asanti-creasing agents, in producing laminated articles and for numerousother purposes. The liquid intermediate condensation products also maybe used directly as casting resins. Those intermediate products of agel-like nature may be dried and granulated to form clear, unfilled,heat-convertible resins.

In order that those skilled in the art better may understand how thisinvention may be carried into efiect, the following examples are givenby way of illustration. All parts are by weight.

Example 1 Parts l-carbamyl guanazole 32.4 Aqueous formaldehyde (approx.37.1%

HCHO) 73.9 Aqueous ammonia (approx. 28% NH3) 3.2 Sodium hydroxide in 2.5parts water 0.05

Chloroacetamide (monochloroiacetamide)- 0.5

All of the above components with the exception of the chloroacetamidewere heated together under reflux at the boiling temperature of the massfor 15 minutes. The chloroacetamide was added to the resulting syrup andrefluxing was continued for an additional minutes to cause thechloroacetamide to intercondense with the l-carbamylguanazole-formaldehyde partial condensation product.

A molding compound was made from the syrupy condensation productcontaining the intercondensed chloroacetamide by mixing it with 35.5parts alpha cellulose in flock form and 0.2 part of a mold lubricant,specifically zinc stearate. The wet compound was dried at 60 C. for 3%hours. A sample of the dried compound was molded at 135 C. for 3 minutesunder a pressure of 2,000 pounds per square inch. The molded piece washard and well cured throughout, was exceptionally light in color and hadexcellent gloss. When this molded piece was tested for Water resistanceby immersing it in boiling water for minutes, it absorbed only 1.7% byweight of water. There was no change in its color or gloss or any othervisible evidence that it had "been afiected in any way by this rigidtest. The

molded piece was uniform and well knitted together and showed goodplastic flow during moldm Example 2 Parts B-N-(para-sulfamyl phenyl)guanazole 55.5 A q u e o u s formaldehyde (approx. 37.1%

HCHO) 53.0

Aqueous ammonia (approx. 28% NHs) 6.5 Sodium hydroxide in 15 parts water0.2 Chloroacetamide 0.5

I All of the above components with the exception of the chloroacetamidewere heated together under reflux at boiling temperature for 30 minutes.The chloroacetamide was now added and refluxing was continued for anadditional 5 minutes. The resulting syrupy condensation prodnot wasmixed with 35 parts alpha cellulose and 0.2 part zinc stearate -to forma molding compound. The wet compound was dried at 60 C. for 1 hour.Well-cured molded pieces having excellent gloss and strength wereproduced by molding samples of the dried compound for 5 minutes at 130C. under a pressure of 2,000 pounds per square inch. Whendichloroacetamide or trichloroacetamide was substituted for themonochloroacetamide in the above formulation, resinous syrups wereobtained that rapidly cured to the insoluble, infusible state whentested at 140 C. on a hot-plate.

Example 3 Parts l-(meta-tolyl) guanazole 143 A q u e o u s formaldehyde(approx. 37.1%

HCHO) 181 Aqueous sodium hydroxide solution (0.46N) 8Monochloroacetamide 2 The above ingredients were heated on a steam platefor about 1 minute to dissolve all the solids and to partly resinify themass. The syrup so obtained was mixed with 105 parts of alpha celamplewas repeated but using 143 parts l-(orthotolyl) guanazole orl-(para-tolyl) guanazole or 169 parts l-(alpha-naphthyl) guanazole or 1-(beta naphthyl) guanazole in place of 143 parts l-(meta-tolyl).guanazole, comparable molded pieces were obtained.

Example 4 Example 5 Parts l-(ortho-tolyl) guanazole 142 A q u e o u sformaldehyde (approx. 37.1%

HCHO) 181 Aqueous sodium hydroxide solution (0.465 N) 8 were heatedtogether for several minutes to yield a clear syrup which separated fromthe aqueous layer. When a sample of this syrup was mixed with from 1 to2% by weight thereof of alpha,

beta-dichloropropionamide and heated on a 135 C. hotplate, the syrupbodied to a resinous mass that upon further heating was converted to acured (insoluble and infusible) state.

Example 6 Same as Example 5 with the exception that from 1 to 2% byweight (of the syrup) of alpha, beta-dibromopropionamide was usedinstead of alpha, beta-dichloropropionamide. The resinous mass curedrapidly to an insoluble, infusible state upon heating on a 135 C.hotplate.

Example 7 Parts l-carbamyl guanazole 107.0 Aqueous formaldehyde (approx.37.1%

HCHO) 486.0 Para-amino benzene sulfonamide 129.0 Sodium hydroxide in 20parts water, 0.4 Chloroacetamide 4.0

All of the above components with the exception of the chloroacetamidewere heated together under reflux at the boiling temperature of the massfor 10 minutes. The chloroacetamide was now added and refluxing wascontinued for lulose in flock form and 2 parts zinc stearate and driedat room temperature. A sample of the dried compound was molded at 135 C.for 5 minutes under a pressure of 3,500 pounds per square an additional3 minutes. A molding (moldable) compound was made by mixing theresulting hot resinous syrup with 241 parts alpha cellulose and 2 partszinc stearate. The wet compound was dried at 60 C. for several hours. Asample of the dried compound was molded for 3 minutes at C. under apressure of 2,000 pounds per square inch. The molded piece was wellcured throughout and showed good plastic flow during molding. Thepara-amino benzene sulfonamide functions as. an intercondensableplasticizer to improve the plasticity of the compound during molding.

Example 8 Parts l-carbamyl guanazole 60.0 Water 1,000.0 Dimethylol urea(containing 11% water) 404.0 Aqueous ammonia (approx. 28% NHa) 6.0Sodium hydroxide in 13 parts water 0.25 Chloroacetamide 3.0

Th same procedure was followed in making the syrup, molding compound andmolded arti-.

ole as described in Example '1 with the exception that the reflux timeafter addition of the chloroaeetamide was 5 minutes and the amount ofalpha cellulose was 1'70 parts. A well-cured molded piece that could bepulled hot from the Aqueous ammonia (approx. 23% N33) 10.0 sodiumhydroxide in 5 parts water 0.1 Urea 48.0

All of the above components were heated together under reflux at theboiling temperature of the mass for minutes. At the end of this reactionperiod 1 part chloroacetamide was added to 115 parts of the syrup andrefluxing was continued for an additional 5 minutes. A molding compoundwas made by mixing the resulting hot resinous syrup with 35 parts alphacellulose and 0.2 part zinc stearate. The wet compound was dried at 65C. for 1 hour. A sample of the dried compound was molded for 5 minutesat 130 C. under a pressure of 2,000 pounds per square inch. The moldedpiece was pulled hot from the mold. It did not become distorted uponcooling to room temperature. It was well cured throughout and had anattractive appearance.

All of the above components were heated together under reflux at boilingtemperature for 30 minutes. To 230 parts of the syrup was added 1 partchloroacetamide. The hot resinous syrup was mixed with 70 parts alphacellulose and 0.4 part zinc stearate to form a molding compound.

The wet compound was dried at 64 C. for 2 hours to yield a moldingcompound that could be satisfactorily molded. A well-cured molded piecewas produced by molding a sample of the pounds per square inch. A moldedpiece that was well cured and homogeneously knit was obtained.

Similar results were obtained when 14.1 parts of l-(para-tolyl)guanazole were substituted for the 13.1 parts l-phenyl guanazole in theabove example.

Example 12 Parts 3-N-(para-sulfamyl phenyl) quanazole. 12.7 Urea 27.0Aqueous formaldehyde (approx.

37.1% HCHO) 31.0 Aqueous ammonia (approx. 28% N113) 2.0 Sodium hydroxidein A parts water 0.08

V Choloroacetamide 0.5

All of the above ingredients with the exception of the chloroacetamidewere heated together under reflux for 30 minutes. The chloroacetamidewas now added to 115 parts of the clear resinous syrup and the refluxingcontinued for" an additional 5 minutes. The resulting hot syrup wasmixed with parts alpha cellulose and 0.2 part zinc stearate to form amolding compound. The wet compound was dried at 60 C. for 1 hour.Well-cured, translucent molded pieces were produced by molding samplesof the dried compound at 130 C. for 5 minutes under a pressure of 2,000pounds per square inch.

Example 13 Parts l-phenyl guanazole 131 dried compound for 5 minutes at130 C. under a pressure of 2,000 pounds per squareinch.

Example 11 Parts l-phenyl guanazole 13.1 Urea 30.0 Aqueous formaldehyde(approx.

37.1% HCHO) 63.0 Aqueous ammonia (approx. 28% NHs) 3.0 Aqueous sodiumhydroxide solution Chloroacetamide 0.2

Formaldehyde-addition product, specifically reformed dimethylol urea(containing 11% water) 404 Water 500 Chloroace 2 were heated togetheruntil the clear solution be-- came milky. The hot syrup was mixed with285 parts alpha cellulose in flock form and 2 parts zinc stearate toform a molding compound. The wet compound was dried at 70 C. A sample ofthe dried compound was molded at C. for 4 minutes under a pressure of3,500 pounds per square inch, yielding an excellently cured moldedarticle that showed good flow characteristics during molding. The moldedpiece did not disintegrate nor show any material change in surfaceappearance when immersed in boiling water for 15 minutes. On anaccelerated test to determine its relative resistance to water, itshowed only 1.2% water'absorption. (The water absorption value isdetermined byimmersing a weighed sample of the molded article for 15minutes in boiling water, immersing immediately in cold water for 5minutes, after which the sample is wiped dry, weighed immediately andthe percentage increase in weight recorded as the per cent water ab- Allof the above components were heated to-' gether for several minutes, bywhich time the resin started to precipitate.

A molding compound was made by mixing the syrup produced as describedabove with 300 parts alpha cellulose and 2 parts zinc stearate. The wetcompound was dried for several hours at 60 assasoa C. -A well-curedmolded piece having good water resistance was obtained by moldinga'sample of the dried compound for 5 minutes at 135 C. under a pressureof 2,000 pounds per square inch. Similar results were obtained when 142parts 1- (ortho-tolyl) guanazole or l-(meta-tolyl) guanazole or 163parts l-(alpha-naphthyl) guanazole or l-(beta-naphthyl) guanazole weresubstituted for the 142 parts l-(para-tolyl) guanazole in the aboveexample- Example 15 Parts l-phenyl guanazole 13.1 Aqueous formaldehyde(approx. 37.1%

HCHO) 18.1 Aqueous sodium hydroxide solution (0.46

N) 0.8 Chloroacetamide -1 0.3

The above ingredients were heated until a resin was obtained that wassolid when cooled to room temperature. The resin was completelydissolved in dioxane and added to another solution containing 20 partsof a polyvinyl acetal, specifically polyvinyl formal, in dioxane. Afterevaporating the solution to dryness, the solid was sheeted ondifferential rolls, the front roll of which was heated at 75 C., until acompletely homogeneous mass was obtained. A sample of the resin wasmolded at 135 C. for 5 minutes at a pressure of 3,500 pounds per squareinch. The mold was cooled before removing the molded piece to preventdistortion since the piece was quite flexible.

Example 16 Parts l-phenyl guanazole 13.1 Aqueous formaldehyde (approx.37.1%

HCHO) 18.1 Aqueous sodium hydroxide solution (0.46

Chloroacetamide i 0.2

were heated together for several minutes. A molding compound was madefrom the resulting syrup by mixing it with 10.5 parts alpha celluloseand 0.2 part zinc stearate. The wet compound was dried at 70 C. A sampleof the dried compound was molded at 135 C. under a pressure of 3,000pounds per square inch for minutes, yielding a well-cured molded articlehaving a smooth, glossy surface appearance. The molding compound showedexcellent flow characteristics during molding. The molded article alsohad excellent water resistance as shown by the fact that, when immersedin boiling water for minutes and then in cold water for 5 minutes, itabsorbed only 1.4% by weight of water.

Example 1? Parts l-(ortho-tolyl) guanazole 142 Aqueous formaldehyde(approx.' 37.1%

HCHO) 181 Aqueous sodium hydroxide solution 0.465

were heated together for several minutes to yield a clear syrup whichseparated from the aqueous layer. When a sample of this syrup was mixedwith from 1 to 2% by weight thereof of chloroacetamide(monochloroacetamide) and heated on a 135 C. hotplate, the syrup bodiedto a resinous mass that upon further heating cured to an insoluble,infusible state. ,When individual samples of the syrup were similarlytreated with dichloroacetamide and trichloroacetamide, the resin wassuch halogenated amides are:

converted to an insoluble and infusible state, although the cure timewas a little longer than with chloroacetamide.

It will be understood, of course, that the halogenated amides mentionedin the above examples are only by way of illustration and that otherhalogenated amides selected from the class consisting of alphahalogenated amides, beta halogenated amides and alpha beta halogenatedamides, which amides contain at least one COHN2 grouping, may be used incarrying this invention into effect. Additional examples of Betadichlorovaleramide Alpha dibromovaleramide Beta dibromovaleramide Alpha,beta dichlorovaleramide Alpha chloromalonic diamide Alpha bromomalonicdiamide Alpha fiuoroadipic diamide Alpha chloromaleic diamide Alphadichloroadipic diamide Beta dichloroadipic diamide Alpha, betadibromopyrotartaric diamide Alpha, beta dichloropyrotartaric diamideAlpha, alpha, alpha" tribromocarballylic triami e Alpha, alpha, alpha"trichlorocarballylic tria- Alpha chloroaceto-acetamide Alphachlorohydantoic amide Alpha bromoaceto-acetamide Alpha bromohydantoicamide Alpha chloro, beta chloro adipic diamide It also will beunderstood that in each of the specific halogenated amides abovementioned the particular halogen shown may be replaced by some otherhalogen, care being taken in the choice of the halogen in the light ofthe properties desired in the final products. For example, whenlight-colored molded articles are desired, the use of iodo derivativesshould be avoided and when the heat-convertible resins are to be used inthe production of molding compositions, the

fiuoro derivatives preferably are avoided. Where a plurality of halogenatoms are present in the halogenated amide, these may be the same ordiii'erent. For example. one halogen in the molecule may be chlorine andanother bromide. In this way it is possible to obtain aheat-convertibleresin or self-curing characteristics and other properties best adaptedto meet a particular molding problem and service application of thefinished article.

'Likewise, it alsowill be understood that the aminotriaaoles named inthe above examples are by way of illustration and that any otheraldehyde-reactable aminotriazole may be employed.

I prefer to use triaaolea containing either at least one unsubstitutedamidogen (-NHs) group or a pluralityoi partly substituted amidogengroups.

' amin'oetriaaoles, e. g. d-p-tolyl 3,5-di-p-tli1idino 1,2,4-triazole,1,4-diphenyl 3-anilino fi-phenylimino 1,2,4-triazole, 2-methyl l-phenylguanazole, l-phenyl 3-am'in0 -methyl 1,2,4-triazole, 2- phenyl S-amino4-methyl 1,2,3-triazole, 1-phenyl guanazole, the 1-tolyl guanazoles, thel-naphthyl guanaaoles, l-phenyi s-amino 1,2,4-triazole, 3,4- diamino,1,2,4-triazole, 2-phenyl 4, 5-diamino 1,2,3-triazole; poly-aminotriazoles wherein the hydrogen atoms of one or all or the amino groupsare partially substituted by other amino groups, e. g., 3,5-dihydrazino4-amino 1,2,4-triazole, 3-hydrazino 5-amino 1,2,4-triazole, 4-hydrazino5- amino 1,2,3-triarolz; etc., polyamino triazoles wherein the hydrogenatoms or one or all oi. the amino groups are partially substitutedbyother monovalent substituents (e. alkyl, aryl, aralkyl, etc.), forinstance l-phenyl S-amino 3-anilino 1,2,4-triazole; l-phenyl 5-amino3-p-toluidino 1,2,4- triazole, 4-p-naphthyl 3,5-di(p-naphthylamino)1,2,4-triazole,'2-phenyl 4-amino 5-acetamino 1,2,4-triazole.

In producing these new condensation products the choice of the aldehydeis dependent largely upon economic considerations and upon theparticular properties desired in the finished product. I prefer to useas the aldehydic reactant formaldehyde or compounds engenderingformaldehyde, e. g., paraformaldehyde, hexamethylene .tetramine, etc.Illustrative examples of otheraldehydes that may be used areacetaldehyde, propionaldehyde, butyraldehyde, acroiein, methacrolein,crotonaldehyde, benzaldehyde. furfural, etc. mixtures thereof, ormixtures of formaldehyde (or compounds engendering formaldehyde) withsuch aldehydes. Illustrative examples of aldehyde-addition products thatmay be used instead of the aldehydes themselves are the monoaridpoly-(N-carbinol) derivatives, more particularly the monoandpoly-methylol derivatives of urea, thiourea, selenourea and iminourea,and of substituted ureas, thioureas, selenoureas and iminoureas(numerous examples of which are given inmy copending application SerialNo. 377,524,'fi1ed February 5, 1941, and assigned to the same assigneeas the present invention), monoand... poly-(N-carbinol) derivatives ofamides of polycarboxylic acids, e. g., maleic, itaconic, Iumarlc,adiplc, malonic, succinic, citric, phthalic, etc., mono andpoly-(N-carbinol) derivatives of amidogentriazines, numerous examples oiwhich are given in my copending application .Berial N o. 377,524.Particularly good results are obtained with active methylene-containingbodies such as monoand di-methylol ureas and the methylol melamines, e.g., mono-,

di trl-, tetro-, pentaand hen-methylol melamines. Monoor poly-(N-carbinol) derivatives, specifically the monoor poly-methylolderivatives, of an aminotriamle as, for instance, a methylol guanazolemay be caused to react with the halogenated amides used in carrying thepresent invention into effect, in which case it is not necessary to usean aminotriarole and an aldehyde as individual starting reactants.Mixtures of aldehydes and aldehyde-addition products may be employed,for example mixtures of formaldehyde and methylol compounds such, forinstance, as dimethylol urea, dimethylol guan-j azole and trimethylolmelamine.

A part of the aminotriaaole reactant may be replaced ii desired by, i'orexample, a urea, e. g., urea (NHaCONHz), thiourea, selenourea,iminourea, and aldehyde-reactable substitution products thereof, e'.g.,, methyl urea, phenyl thiourea,-

etc., by aldehyde-addition products oi a urea, e. g., ,dimethylol urea,etc., or by other organic compounds capableof reacting with an'aldehyde,

. .azole.

e. g., an amino pyrimidyl carbamyl-alkyl sulfide. Numerous examples ofcompounds embraced by the term a urea" are given in my copendingapplication Serial No. 289,277. I may use either a single or a pluralityof halogenated amides with the aminotriazole reactant or with theaminotriazole and urea reactants. Various aminodiazines, aminodiazolesor aminot'riazines maybe used in place of a part of the aminotriazole.

The ratio oi? the aldehydic reactant to the aminotriazole may beconsiderably varied but, in general, it is desirable to use at least'onemol of an aldehyde for each mol of aminotriazole. In producing theheat-convertible resinous condensation products of this invention, theproportion of the halogenated amide in all cases is at least sufllcientto render the resin convertible under-heat to an insoluble, infusiblestate. Ordinarily not exceeding substantially as mol halogenated amideis used for each mol of aminotri- No advantage accrues from using anamount of halogenated amide above the minimum required to secure thedesired curing rate. Further, the use ofhigher amounts of halogenatedamideis undesirable for most molding ap-,

plications because 01 the greater diiliculty in obtaining moldedarticles of suitable hardness, but may not be objectionable ,for otherapplications of the material. Also, in some cases, particularly wherehigh molecular weight halogenated amides as for example alphachlorostearamide are used, the amide part of the resin molecule exceedson a weight basis the aminotriazole por- 'tion of the molecule.Consequently, in such cases the inherent characteristics (for example,waxy particular .molratio of halogenated amide to the other componentsis dependent somewhat upon the inherent characteristics and otherproperties desired in the heat-curable and heatcured resinouscondensation products. The aldehydic reactant may be used, for example,in an amount corresponding to from one to five or six mols thereof foreach mol oi aminotriazole.

Good results usually are obtained by using from 1 to 3% mols ofaldehyde, specifically formaldehyde, for each mol of aminotriazole.Taking l-amino guanazole (an aminotriazole containing threeunsubstituted amidogen groups) as illustrative of the aminotriazole,particularly good results are obtained with approximately three molsaldehyde, e. g., formaldehyde, for each mol l-amino guanazole. If theaminotriazole contains only two unsubstituted amidogen groups (or oneunsubstituted and two partly substituted amidogen groups), then oneadvantageously may use approximately two mols aldehyde for each mol ofaminotriazole. If the aminotriazole contains only one unsubstitutedamidogen group (or two partly substituted amidogen groups), then noparticular advantage usually accrues from using much in excess of onemol aldehyde for each mol of such an aminotriazole. When the aldehyde isavailable for reaction in the form of an. aldehyde-addition productsuch, for instance, as dimethylol urea, trimethylol melamine, etc., thenhigher amounts of such aldehyde-addition products ordinarily are used,for example, up to ten or twelve mols of such aldehyde-addition productfor each mol of the aminotriazole.

When an aldehyde-addition product of an aminotriazole, e. g., a methylolguanazole as for instance dimethylol guanazole, is used as a reactantwith a halogenated amide of the liind with which this invention isconcerned, such aldehyde-addition product functions in a dual capacityin that it provides a source for the introduction of both anaminotriazole and an alkylene bridge, e. g., CH2-, into the resinmolecule. The aldehyde-addition product may be used alone or togetherwith an aminotriazole, or with an aldehyde or with both an aldehyde andan aminotriazole.

The properties of the fundamental resins of this invention may be variedwidely by introducing other modifying bodies before," during or aftereffecting condensation between the primary components. Thus, asmodifying agents I may use, for instance, monohydric alcohols such asethyl, propyl, isopropyl, butyl, isobutyl, hexyl,

etc., alcohols; polyhydric alcohols such as ethylene glycol, diethyleneglycol, glycerine, pentaerythritol, polyvinyl alcohol, etc.; amides suchas formamide, acetamide, stear'amide, acrylamide, benzamide, toluenesulfonamides, benzene disulfonamides and trisulfonamides, adipicdiamide, phthalamide, etc.; amines, e. g., ethylene diamine, aniline,phenylene diamine, etc.; phenol and substituted phenols, e. g., theaminophenols, the cresols, the xylenols, the tertiary alkyl phenols andother phenols such as mentioned in my Patent 2,239,441; ketones;nitriles, e. g., acrylonitrile, methacrylonitrile, succinonitrile, etc.;and others. Those modifying agents whic are reactable with theaminotriazole, or with the aldehyde or with the reaction product of theaminotriazole and the aldehyde (that is, an aldehyde-addition productvof the aminotriazole, e. g,, dimethylol guanazole) may be incorporatedinto the composition by mixing all the reactants and effectingcondensation therebetween or by various permutations of the reactants asdescribed,- for example, in my Patent 2,239,441 with particularreference to reactions involving a phenol, an aliphatic aldehyde and amalonic compound (page 3, column 1, lines 224) wood products. formalizedcellulose derivatives,

.lignin, protein-aldehyde condensation products,

resinous reaction products of aldehydes, for example formaldehyde, withthe aminotriazines (e. g., melamine, ammeline, etc.), alone or admixedwith, for example, urea, guanazole, or urea and guanazole, resinsobtained by reaction of an aldehyde with the aminodiazines (e. g., 2, 4,6- triaminopyrimidine', 2,4-diaminoquinazoline, etc.) or with theaminodiazoles, alone or admixed with, for example, urea, melamineor ureaand melamine. Other examples of modifying bodies are the urea-aldehydecondensation products, the aniline-aldehyde condensation products,furfural condensation products, phenol-aldehyde condensation products,modified or unmodified, saturated or unsaturated polyhydric alcohol-poboxylic acid condensation products, water-soluble cellulose derivatives,natural gums and resins such as shellac, rosin, etc.; polyvinylcompounds such as polyvinyl esters, e. g., polyvinyl acetate,

polyvinyl butyrate, etc., polyvinyl ethers including polyvinyl acetals,specifically polyvinyl formal, etc.

Dyes, pigments, plasticizers, mold lubricants, opacifiers and variousfillers (e. g., wood flour, glass fibers, asbestos, including defibratedasbestos, mineral wool, mica, cloth cuttings, etc.) may be compoundedwith the resin in accordance with conventional practice to providemolding composltions best fitted to yield molded articles of optimumproperties for the particular service application.

The molding compositions of this invention may be molded into a varietyof shapes under heat and pressure, more particularly at temperatures ofthe order of to 200 C., preferably from to 180 C. Molding pressures maybe varied considerably, but usually are within the range of 1,000 to10,000 pounds per square inch, more particularly from 2,000 to 4,000 or5,000 pounds per square inch.

From the foregoing description it will be seen that the presentinvention provides new and useful compositions of matter comprising aconden- -CONH: grouping. 'The scope of the invention also includesmethod features for the production of such condensation products. Forinstance,

, one method feature of the invention comprises The modifying bodiesalso may take the form of high molecular weight bodies with or withoutresinous characteristics, for example hydrolyzed effecting partialreaction between ingredients comprising an aminotriazole, specifically aguanazole, and an aldehyde, e. g., formaldehyde (or ingredientscomprising a urea, specifically NHzCONHz, an aminotriazol'e and analdehyde) in the presence of an alkaline condensation catalyst,specifically a condensation catalyst comprising ammonia and a fixedalkali, adding a small amount of one or more of the herein describedhalogenated amides, e. g., a halogenated acetamide such as a mono-, diortri-chloroacetamide or mixtures thereof, mono-, diortri-bromoacetamides-or mixtures thereof, etc., to the resulting partialcondensation product and causing thehalog'enated amide to intercondensewith the said partial condensation product. My invention also providesthermosetting (heat-hardenable) molding compositions comprising afiller,

'losis materials in sheet or other form.

- uct of reaction under heat of e. g., a cellulosic filler, and aheat-curable condensation product of this invention, e. g., aheathardenable (heat-curable) condensation product of ingredientscomprising a guanazole (or urea and a guanazole), formaldehyde orcompounds engendering formaldehyde, and an alpha, a beta or an alpha andbeta halogenated amide having in its molecule at least one CONH2grouping, as well as molded articles of manufacture comprising theheat-set molding compositions.

The modified and unmodified resinous compositions of this invention havea wide variety of uses. For example, in addition to their use in theproduction of molding compositions, they may be employed as modifiers ofother natural and synthetic resins, as laminating varnishes in theproduction of laminated articles wherein sheet materials, e. g., paper,cloth, sheet asbestos, etc., are coated and impregnated with the resin,superimposed and thereafter united under heat and pressure. They may beused in the production of wire or baking enamels from which insulatedwires and other coated products are made, for bonding or cementingtogether mica flakes to form a laminated mica article, for bondingtogether abrasive grains in the production of resinbonded abrasivearticles such, for instance, as grindstones, sandpapers, etc., in themanufacture of electrical resistors, etc. They also may be employed fortreating cotton, linen and other cellu- They also may be used asimpregnants for electrical coils and for other electrically insulatingapplications. v

This application is a continuation-in-part of my copending applicationSerial No. 289,277, filed August 9, 1939, and assigned to the sameassignee as the present invention.

What I claim as new and desire to secure by Letters Patent of the UnitedStates is:

1. A composition of matter comprising the condensation product ofingredients comprising an aminotriazole, an aldehyde and a halogenatedamide selected from the class consisting of alpha halogenated amides,beta halogenated amides and. alpha beta halogenated amides, which amidescontain at least one CONH-2 grouping.

2. A composition as in claim 1 wherein the condensation product is analcohol-modified condensation product of the stated components.

3. A composition as in claim 1 wherein the aminotriazole is a guanazole.

4. A heat-curable resinous condensation product of ingredientscomprising an aminotriazole, formaldehyde and a halogenated amideselected from the class consisting of alpha halogenated amides, betahalogenated amides and alpha beta halogenated amides, which amidescontain at least one CONH2 grouping.

5. A product comprising the cured condensation product of claim 4.

6. A composition comprising the product or reaction under heat of (1) apartial condensation product of ingredients comprising azole and analdehyde and (2) a halogenated amide selected from the class consistingof alpha halogenated amides, beta halogenated amides and alpha betahalogenated amides, which amides contain at least one CONH2 grouping.

-'l. A resinous composition comprising the prod- (1) a partialcondensation product obtained by reaction, while admixed with analkaline substance, of ingrediresinous an aminotriand (2) a halogenatedamide selected from the class consisting of alpha halogenated amides,

. nated amides and ents comprising a guanaz'ole and formaldehyde, I

beta halogenated amides and alpha beta halogenated amides, which amidescontain at least one -CONH grouping.

8. A resinous composition comprising the product of reaction under heatof (l) a partial condensation product obtained by reaction, whileadmixed with a condensation -catalyst comprising ammonia and a fixedalkali, of ingredients comprising a guanazole and formaldehyde, and (2)a halogenated acetamide.

9. A resinous composition obtained by condensation of ingredientscomprising l-phenyl guanazole, formaldehyde and a chlorinated acetamide.

A resinous composition comprising the product of condensation ofingredients comprising urea, l-phenyl guanazole, formaldehyde andmonochloroacetamide.

11. A composition comprising the product of condensation of ingredientscomprising amethylol guanazole and a halogenated amide selected from theclass consisting of alpha halogenated amides, beta halogenated amidesand alpha beta halogenated amides, which amides contain at least oneCONH2 grouping.

12. A composition comprising the resinous product of condensation ofingredients comprising an aminotriazole, dimethylol urea and 9.halogenated amide selected from the class consisting of alphahalogenated amides, beta halogealpha beta halogenated amides, whichamides contain at least one --CONHz grouping.

13. A resinous composition comprising the product of condensation ofingredients comprising a guanazole, dimethylol urea and a chlorinatedacetamide.

14. A heat-curable resinous condensation product of ingredientscomprising urea, l-phenyl guanazole, formaldehyde and a halogenatedamide selected from the class consisting of alpha halogenated amides,beta halogenated amides and alpha beta halogenated amides, which amidescontain at least one -CONH2 grouping.

15. A product comprising the cured resinous condensation product ofclaim it.

16. A thermosetting molding composition comprising a filler and aheat-hardenableresinous condensation product of ingredients comprisingan aminotriazole, formaldehyde and a chlorinated acetamide.

17. An article ofmanufacture comprising the heat-set molding compositionof claim 16.

18. A method of preparing new condensation products which comprisesefiecting a condensation reaction between. ingredients comprising anaminotriazole, an aldehyde and a halogenated amide selected from theclass consisting of alpha halogenated amides, beta halogenated amidesand alpha beta halogenated amides, which amides contain at least oneCONH: grouping.

19. The method which comprises effecting partial condensation betweeningredients comprising a guanazole, urea and formaldehyde in thepresence of a condensation catalyst comprising ammonia and a fixedalkali, adding a small amount of a chlorinated acetamide to theresulting partial condensation product, and causing the chlo- ICERTIFICATE OF CORRECTION. Patent No 2, 552, 5.0;. October 19, 191

' (ammo F. DIALELIOA.

It is hereby certified that error appears in the printed specifioetionof the above numbered patent hequiring correction as follows: Page 1,first column; line 145, for "contained" read' -containandeecond column,lines 1 and 2, for 'ami-iaotril.azolealdehydereed..--am1noti\1azo1e-a1dehyde line 2, for by" read -be--; page 2 firsteo11fin1, l'ine h 6,- for "rotonic" read --crotonic--- page 5,-secondcolumn, line 11-12., for 'monochloroeeetamile I read---monochloroacetmnide--; beg H fix-shoeing, lihee. 12 and 15; strikeout "(approx 27.1% 116110 'i1ne 68'and second 901m line 10 forFQuanazoI'e" read --guanazo1e same page, second co11mn, .l1ne 35, for"reformed" reed -:Lng parenthesis; and second golumn, line IIQ'for-FCOHNread-e 60N112 -page.6, Vfi'rst column; line 2, .for "bromide" read"brominelinee and l .O, .efter "e. g. insert a oomma; lihe 51,- strikeout the comma after "dim uino' fiiis toecurrence; and e cond column,line 5, for '-'tetr read-- tetraand that the said Lette're 'Pafientshould be reed with this correction therein that the same may conform tothe record of the ease in the Patent Offiee.

sigma and sealed this Am day 1 Janue ry, A. 1:;- 191m.

Henry Van A redale, (Seal) Acting Gommigeioner oi Patents.

